US5106914A - Pressure sensitive adhesive compositions and elements made therefrom - Google Patents
Pressure sensitive adhesive compositions and elements made therefrom Download PDFInfo
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- US5106914A US5106914A US07/770,977 US77097791A US5106914A US 5106914 A US5106914 A US 5106914A US 77097791 A US77097791 A US 77097791A US 5106914 A US5106914 A US 5106914A
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title 1
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 239000000853 adhesive Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003906 humectant Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical class CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 abstract description 12
- -1 skin Substances 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000000123 paper Substances 0.000 abstract description 5
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000012790 confirmation Methods 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 230000001235 sensitizing effect Effects 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 13
- 238000009472 formulation Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920000847 nonoxynol Polymers 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001353 Dextrin Polymers 0.000 description 4
- 239000004375 Dextrin Substances 0.000 description 4
- 235000019425 dextrin Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BLXVTZPGEOGTGG-UHFFFAOYSA-N 2-[2-(4-nonylphenoxy)ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCO)C=C1 BLXVTZPGEOGTGG-UHFFFAOYSA-N 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- KWVPFECTOKLOBL-KTKRTIGZSA-N 2-[(z)-octadec-9-enoxy]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCO KWVPFECTOKLOBL-KTKRTIGZSA-N 0.000 description 1
- PITRRWWILGYENJ-UHFFFAOYSA-N 2-[2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCO)C=C1 PITRRWWILGYENJ-UHFFFAOYSA-N 0.000 description 1
- WIHIUFRJMOAJFO-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 WIHIUFRJMOAJFO-UHFFFAOYSA-N 0.000 description 1
- JYCQQPHGFMYQCF-UHFFFAOYSA-N 4-tert-Octylphenol monoethoxylate Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCO)C=C1 JYCQQPHGFMYQCF-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HDKLIZDXVUCLHQ-UHFFFAOYSA-N non-3-en-2-one Chemical compound CCCCCC=CC(C)=O HDKLIZDXVUCLHQ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- 239000012976 trial formulation Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Definitions
- This invention relates to adhesive compositions and methods for manufacture thereof, which compositions are easily formable to shape and are suitable for use in surgical, medical, and industrial applications.
- compositions which are suitable for medical use and in particular, adapted to be used for ostomy appliances are disclosed in the patent literature. (See U.S. Pat. No. 4,393,080.) Generally, such compositions require resistance to erosion by moisture or other biological fluids, must exhibit good adherence to the human skin, and also must not be irritating. In addition, it is desired to have adhesive compositions for various industrial and medical applications, which are easily shaped so as to conform to the contours of the surface to which they are being applied and yet are simple to prepare.
- the hydrolysis product would be the diacid whereas the esterification product may be the partial or full ester according to the following sequence: ##STR2## wherein R may be a wide variety of organic groups, e.g.,
- alkyl polyethoxylates aromatics, and fused aromatics, since the most important characteristic of the R-OH compounds is the hydroxyl group.
- the masses or elements may have varying degrees of tack, shear, and peel strength.
- the masses can be formed within a container, which allows shaping of the element, which also provides packaging for the adhesive until its use.
- the methylvinyl ether/maleic anhydride co-polymer first component which is suitable for use in the present invention includes polymers wherein n is such that the weight average molecular weight is in the range from about 1.25 ⁇ 10 6 to 2.4 ⁇ 10 6 and most preferably, from about 1.08 ⁇ 10 6 to 1.98 ⁇ 10 6 .
- Gantrez GAF Chemical Corporation
- the preferred materials for the first component are the long chain methylvinyl ether/maleic anhydride co-polymers wherein the maleic anhydride moiety in the polymer is intact, e.g., Gantrez S-97, and Gantrez AN-169.
- the second component used to form the composition is an hydroxylated compound which serves to hydrolyse or esterify the polymer.
- Typical of such hydroxylated compounds are polyethoxylated fatty alcohols, oleyl alcohols, nonyl phenols, and octyl phenols.
- Others include polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol.
- the amount of the first component reactant used for the reaction is in the range from about 5 to 50 weight %. Preferred is from about 10 to 40 weight %, and most preferred is from about 15 to 35 weight %; all percentages being based on the total weight of the reactants.
- the amount of hydroxylated compound used for the reaction in the present invention is in the range from about 5 to 50 weight % and preferably, from about 10 to 35 weight %, and most preferably, from about 15 to 30 weight % based on the total weight of the composition.
- composition may employ various additives, e.g., humectants, fillers, and the like.
- additives e.g., humectants, fillers, and the like.
- Humectants are particularly useful since they serve to prevent the finally prepared element from drying out.
- Such humectants include non-ionic surfactants as well as certain compounds within the class of hydroxylated compounds which are useful to the second component, e.g., glycerol and polyethylene glycol.
- the second component may act as both a reactant and humectant.
- the amount of humectant generally is in the range from about 5 to 50 weight %, preferably from about 15 to 35 weight %, and most preferably, from about 20 to 25 weight %, all weight percents being based on the total weight of the composition. Generally, the remainder of the reaction mixture is water.
- the inventive composition may be prepared by particularly advantageous.
- the methylvinyl ether/maleic anhydride co-polymer first component and hydroxylated compound second component, and water are reacted by admixing with stirring and heating to form a smooth paste. This reaction is generally carried out at a temperature from about 25° to 95° C.
- the hydroxylated compound, first component humectant (if used, and if different from the hydroxylated compound) are first mixed together with water.
- the mixture is warmed to a temperature in the range from about 25° to 70° C., preferably, from about 50° to 70° C., and, most preferably, about 60° C., and then the methylvinyl ether/maleic anhydride copolymer first component is added with stirring. Normally, this admixing is carried out slowly, i.e., over a period of from about 15 to 20 minutes to ensure uniformity of the mixture and to form a smooth paste.
- the reaction mass is heated at a temperature and for a time period sufficient to effect completion of the reaction which it is generally evidenced by the formation of a cohesive, adhesive element.
- the reaction is carried out at a temperature from about 70° to 95° C., preferably, from about 85° to 95° C., and most preferably, from about 90° to 95° C., for about 0.5 to 6 hours, preferably, from about 1 to 2 hours, and most preferably, for one hour.
- This heating should be carried out so as to assure a uniform temperature throughout the reaction mixture and avoid localized heating.
- the paste is placed in a mold having the desired shape of the element and the reaction is carried out in the mold thus producing a finished adhesive element having the desired shape.
- the inventive adhesive mass is formed by mixing the reactants (paste) in a flexible bag or container of a plastic film, e.g., polyethylene.
- a plastic film e.g., polyethylene.
- the advantage is that the reaction may be formulated within the bag or enclosure, and then shaped while in the bag.
- the reactants in the shaped bag may be subjected to the reaction conditions and, upon cooling, the element is ready for use by removal from the bag at the time of use. Consequently, in essentially a series of simple steps, the adhesive can be formulated in a manner which allows it to be stored in its own packaging and one need only remove the mass from the packaging at the time of use.
- Gantrez AN-119 a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 200,000
- Gantrez AN-139 a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 1,000,000
- Gantrez AN-169 a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 2,000,000
- Antarox DM-970 dialkylnonyl phenol ethoxylate
- Pegol F-68 propylene oxide/ethylene oxide co-polymer with a ratio of 80/20
- Pegol L-61 propylene oxide/ethylene oxide co-polymer with a ratio of 90/10
- Emulphor ON-870 oleyl alcohol polyoxyethylated with 20 mols/mole of ethylene oxide
- Gafac LO-529 phosphate ester of ethoxylated nonylphenol
- Pegol 400 polyethylene glycol with a molecular weight of 400
- Pegol 1450 polyethylene glycol with a molecular weight of 1450
- Pegol 4000 polyethylene glycol with a molecular weight of 4000
- Dextrin 30 AN 45 degraded starch
- Igepal CO-210 ethoxylated nonylphenol with a molecular weight of 286
- Igepal CO-520 ethoxylated nonylphenol with a molecular weight of 440
- Igepal CO-610 ethoxylated nonylphenol with a molecular weight of 528-572
- Igepal CO-630 ethoxylated nonylphenol with a molecular weight of 616
- Igepal CO-720 ethoxylated nonylphenol with a molecular weight of 748
- Igepal CO-880 ethoxylated nonylphenol with a molecular weight of 1540
- Igepal CO-990 ethoxylated nonylphenol with a molecular weight of 4620
- Igepal CA-630 ethoxylated nonylphenol with a molecular weight of 621
- a variety of samples were obtained by using different amounts of water, glycerol, surfactant, and methyl-vinyl ether/maleic anhydride co-polymer.
- the indicated amount of water, glycerol, and surfactant were introduced to a glass beaker which was heated in a water bath to 60° C. with stirring.
- the methylvinyl ether/maleic anhydride copolymer was added to this mixture with stirring. After a smooth paste was formed, the mixture was placed in a polyethylene 5" ⁇ 8" freezer bag (polyethylene thickness of 35-40 micrometers).
- the bag was flattened lightly between two glass plates secured with elastic bands, the bag was sealed and immersed in a water bath at a temperature of about 90° to 95° C. for at least one hour. After heating, the bag was removed and cooled with tap water. The mass was sampled by cutting a strip from the edge and then removing one or both sides of the attached polyethylene film to provide the adhesive test piece.
- Adhesion to various surfaces was tested by applying a 1/16 inch mass formed by the above-outlined procedure to skin, glass, paper, gauze dressing, applying slight finger pressure to attach and then attempting to remove the mass as indicated.
- Table I shows the compositions of 6 different formulations produced by the above-outlined method.
- Table II shows the properties of each of these formulations.
- Tables III and IV show the compositions and properties of a variety of samples prepared using additional hydroxyl-containing polymers and compounds.
- Tables V and VI show yet a further variety of samples in accordance with the present invention and the properties thereof.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
An adhesive element which exhibits excellent properties with respect to a variety of substrates, such as, skin, glass, fabric, paper, plastic, and other non-porous surfaces which is non-toxic, and non-sensitizing. The element exhibits high cohesive strength so that its integrity is maintained on removal from the substrate leaving no residues and is highly flexible so that total confirmation with the underlying shape of the substrate is maintained. The adhesive composition is the hydrolysis or esterification product of a methylvinyl ether/maleic anhydride co-polymer with an hydroxylated compound. Methods for preparation of the inventive adhesive element are disclosed.
Description
This is a division of application Ser. No. 07/455,953, filed Dec. 22, 1989.
I. Field of the Invention
This invention relates to adhesive compositions and methods for manufacture thereof, which compositions are easily formable to shape and are suitable for use in surgical, medical, and industrial applications.
II. Description of the Prior Art
Various adhesive compositions which are suitable for medical use and in particular, adapted to be used for ostomy appliances are disclosed in the patent literature. (See U.S. Pat. No. 4,393,080.) Generally, such compositions require resistance to erosion by moisture or other biological fluids, must exhibit good adherence to the human skin, and also must not be irritating. In addition, it is desired to have adhesive compositions for various industrial and medical applications, which are easily shaped so as to conform to the contours of the surface to which they are being applied and yet are simple to prepare.
Attempts to formulate such compositions utilizing mixtures of various polymers and hydroxyl-containing compounds, such as, Gantrez (a product of GAF Chemical Corporation composed of a co-polymer of methylvinyl ether and maleic anhydride), polyethylene oxide, ethoxylated alkyl phenol or nonyl phenol, e.g., Igepal, polyethylene oxide (GAF Chemical) are known. (See Japanese Patent 8805757, German Patent 3039542, and German Patent 2311746.) However, improvements in such adhesive elements are in constant demand, particularly, with respect to exhibiting the concomitant properties of good adhesion to the surface, ability to conform to the surface and yet absence of irritation in medical applications.
We have discovered an adhesive element which exhibits highly desirable properties with respect to the above-outlined requirements. In particular, we have discovered a method for making such an adhesive element by hydrolysing or esterifying a co-polymer of polymethylvinyl ether and maleic anhydride having the formula: ##STR1## wherein n is such that the weight average molecular weight is from about 2×105 to 2.4×106 to form a smooth paste. The paste may then be formed into the desired shape and heated for a period of time and temperature sufficient to form a gel. Upon cooling, a formed adhesive mass or element is obtained in the particular desired shape which is suitable for use in medicinal as well as other end uses.
More particularly, we have discovered a variety of adhesive masses or elements which may be useful in many different medical devices and can be easily formed into desired shapes by reacting slurries of a first component comprising the methylvinyl ether/maleic anhydride co-polymer with a second component comprising an hydroxylated compound to hydrolyse or esterify the co-polymer.
Typically, the hydrolysis product would be the diacid whereas the esterification product may be the partial or full ester according to the following sequence: ##STR2## wherein R may be a wide variety of organic groups, e.g.,
alkyl polyethoxylates, aromatics, and fused aromatics, since the most important characteristic of the R-OH compounds is the hydroxyl group.
Depending upon the particular hydrolysing or esterification compounds used, the masses or elements may have varying degrees of tack, shear, and peel strength. Moreover, in a preferred embodiment, the masses can be formed within a container, which allows shaping of the element, which also provides packaging for the adhesive until its use.
Preferably, the methylvinyl ether/maleic anhydride co-polymer first component which is suitable for use in the present invention includes polymers wherein n is such that the weight average molecular weight is in the range from about 1.25×106 to 2.4×106 and most preferably, from about 1.08×106 to 1.98×106. A wide variety of such co-polymers are marketed under the trademark Gantrez (GAF Chemical Corporation).
The preferred materials for the first component are the long chain methylvinyl ether/maleic anhydride co-polymers wherein the maleic anhydride moiety in the polymer is intact, e.g., Gantrez S-97, and Gantrez AN-169.
The second component used to form the composition is an hydroxylated compound which serves to hydrolyse or esterify the polymer. Typical of such hydroxylated compounds are polyethoxylated fatty alcohols, oleyl alcohols, nonyl phenols, and octyl phenols. Others include polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol.
The amount of the first component reactant used for the reaction is in the range from about 5 to 50 weight %. Preferred is from about 10 to 40 weight %, and most preferred is from about 15 to 35 weight %; all percentages being based on the total weight of the reactants.
The amount of hydroxylated compound used for the reaction in the present invention is in the range from about 5 to 50 weight % and preferably, from about 10 to 35 weight %, and most preferably, from about 15 to 30 weight % based on the total weight of the composition.
In addition, the composition may employ various additives, e.g., humectants, fillers, and the like.
Humectants are particularly useful since they serve to prevent the finally prepared element from drying out. Such humectants include non-ionic surfactants as well as certain compounds within the class of hydroxylated compounds which are useful to the second component, e.g., glycerol and polyethylene glycol. Thus, in this case, the second component may act as both a reactant and humectant.
The amount of humectant generally is in the range from about 5 to 50 weight %, preferably from about 15 to 35 weight %, and most preferably, from about 20 to 25 weight %, all weight percents being based on the total weight of the composition. Generally, the remainder of the reaction mixture is water.
The manner in which the inventive composition may be prepared is particularly advantageous. Generally, the methylvinyl ether/maleic anhydride co-polymer first component and hydroxylated compound second component, and water are reacted by admixing with stirring and heating to form a smooth paste. This reaction is generally carried out at a temperature from about 25° to 95° C. In a preferred embodiment, the hydroxylated compound, first component humectant (if used, and if different from the hydroxylated compound) are first mixed together with water. The mixture is warmed to a temperature in the range from about 25° to 70° C., preferably, from about 50° to 70° C., and, most preferably, about 60° C., and then the methylvinyl ether/maleic anhydride copolymer first component is added with stirring. Normally, this admixing is carried out slowly, i.e., over a period of from about 15 to 20 minutes to ensure uniformity of the mixture and to form a smooth paste.
After the addition of the first component, the reaction mass is heated at a temperature and for a time period sufficient to effect completion of the reaction which it is generally evidenced by the formation of a cohesive, adhesive element. Generally the reaction is carried out at a temperature from about 70° to 95° C., preferably, from about 85° to 95° C., and most preferably, from about 90° to 95° C., for about 0.5 to 6 hours, preferably, from about 1 to 2 hours, and most preferably, for one hour. This heating should be carried out so as to assure a uniform temperature throughout the reaction mixture and avoid localized heating. Advantageously, the paste is placed in a mold having the desired shape of the element and the reaction is carried out in the mold thus producing a finished adhesive element having the desired shape.
Preferably, the inventive adhesive mass is formed by mixing the reactants (paste) in a flexible bag or container of a plastic film, e.g., polyethylene. The advantage is that the reaction may be formulated within the bag or enclosure, and then shaped while in the bag. The reactants in the shaped bag may be subjected to the reaction conditions and, upon cooling, the element is ready for use by removal from the bag at the time of use. Consequently, in essentially a series of simple steps, the adhesive can be formulated in a manner which allows it to be stored in its own packaging and one need only remove the mass from the packaging at the time of use.
The following are the chemical names of the trademark products used in the Examples:
Gantrez AN-119: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 200,000
Gantrez AN-139: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 1,000,000
Gantrez AN-169: a co-polymer of methylvinyl ether and maleic anhydride with a molecular weight of 2,000,000
Antarox DM-970: dialkylnonyl phenol ethoxylate
Pegol F-68: propylene oxide/ethylene oxide co-polymer with a ratio of 80/20
Pegol L-61: propylene oxide/ethylene oxide co-polymer with a ratio of 90/10
Emulphor ON-870: oleyl alcohol polyoxyethylated with 20 mols/mole of ethylene oxide
Gafac LO-529: phosphate ester of ethoxylated nonylphenol
Pegol 400: polyethylene glycol with a molecular weight of 400
Pegol 1450: polyethylene glycol with a molecular weight of 1450
Pegol 4000: polyethylene glycol with a molecular weight of 4000
Dextrin 30 AN 45: degraded starch
Igepal CO-210: ethoxylated nonylphenol with a molecular weight of 286
Igepal CO-520: ethoxylated nonylphenol with a molecular weight of 440
Igepal CO-610: ethoxylated nonylphenol with a molecular weight of 528-572
Igepal CO-630: ethoxylated nonylphenol with a molecular weight of 616
Igepal CO-720: ethoxylated nonylphenol with a molecular weight of 748
Igepal CO-880: ethoxylated nonylphenol with a molecular weight of 1540
Igepal CO-990: ethoxylated nonylphenol with a molecular weight of 4620
Igepal CA-630: ethoxylated nonylphenol with a molecular weight of 621
The following example illustrates the invention:
A variety of samples were obtained by using different amounts of water, glycerol, surfactant, and methyl-vinyl ether/maleic anhydride co-polymer. The indicated amount of water, glycerol, and surfactant were introduced to a glass beaker which was heated in a water bath to 60° C. with stirring. The methylvinyl ether/maleic anhydride copolymer was added to this mixture with stirring. After a smooth paste was formed, the mixture was placed in a polyethylene 5"×8" freezer bag (polyethylene thickness of 35-40 micrometers).
The bag was flattened lightly between two glass plates secured with elastic bands, the bag was sealed and immersed in a water bath at a temperature of about 90° to 95° C. for at least one hour. After heating, the bag was removed and cooled with tap water. The mass was sampled by cutting a strip from the edge and then removing one or both sides of the attached polyethylene film to provide the adhesive test piece.
Adhesion to various surfaces was tested by applying a 1/16 inch mass formed by the above-outlined procedure to skin, glass, paper, gauze dressing, applying slight finger pressure to attach and then attempting to remove the mass as indicated.
Values assigned, i.e., good, fair poor, where judged as follows:
good--masses remain adhered to the substrate and can only be removed by peeling from said substrate by applying some force
fair--same procedure but mass easily removed with little applied force
poor--same procedure but mass peels from substrate with little or no applied peeling force (literally falls off the substrate of its own weight).
Table I shows the compositions of 6 different formulations produced by the above-outlined method. Table II shows the properties of each of these formulations.
As can be seen from the following examples, depending on the relative amounts and specific compounds or reactants used within the scope of the classes of components described herein in accordance with the invention, a wide variety of tack and adhesive properties can be obtained which allows the element to be tailored for a particular end use.
TABLE I
______________________________________
INITIAL TRIAL FORMULATIONS
Raw Sample Material
1 2 3 4 5 6
______________________________________
Gantrez AN-119 25 -- -- -- -- --
Gantrez AN-169 -- 25 20 20 25 25
Glycerol -- 5 20 20 25 25
Pegol F-68 -- 25 -- 20 25 --
Igepal CO-720 25 -- -- -- -- --
Igepal DM-970 -- -- -- -- -- 25
Water 30 35 -- -- 25 25
______________________________________
TABLE II
__________________________________________________________________________
Adhesion
to skin Adhesion
Skin- Skin-
After
Adhesion
Adhesion
to removal
reseal
Formulation
Initial
4 hours
to glass
to paper
dressing
properties
properties
__________________________________________________________________________
1 good
good
-- -- -- -- --
2 fair
poor
-- -- -- -- --
3 poor
poor
-- -- -- -- --
4 poor
poor
-- -- -- -- --
5 fair
poor
-- -- -- -- --
6 good
good
-- -- -- -- --
These formulations were repeated at a later date when the
successful formulations produced equally satisfactory results
__________________________________________________________________________
Tables III and IV show the compositions and properties of a variety of samples prepared using additional hydroxyl-containing polymers and compounds.
TABLE III
______________________________________
ALTERNATIVE HYDROXYL COMPOUNDS
A trial series was next made to investigate the suitability of other
--OH containing polymers and compounds.
Raw Sample Material
7 8 9 10 11 12 13 14
______________________________________
Gantrez AN-169
25 25 25 25 25 25 25 25
Water 25 25 25 17 34 34 25 34
Glycerol 25 25 25 25 25 -- -- --
Igepal CO-210
25 -- -- -- -- -- -- --
Igepal CO-610
-- 25 -- -- -- -- -- --
Pegol L-61 -- -- 25 -- -- -- -- --
Pegol 1450 -- -- -- -- -- 25 -- --
Dextrin 30 AN 45
-- -- -- -- -- -- -- 25
______________________________________
TABLE IV
__________________________________________________________________________
Adhesion
to skin Adhesion
Skin- Skin-
After
Adhesion
Adhesion
to removal
reseal
Formulation
Initial
4 hours
to glass
to paper
dressing
properties
properties
__________________________________________________________________________
7 fair
fair
good -- -- easy --
8 good
good
good good good -- --
9 fair
fair
good -- -- -- --
10 poor
poor
-- -- -- -- --
11 good
good
good good good fair --
12 good
good
good -- -- -- --
13 poor
poor
-- -- -- -- --
14 good
good
good -- -- poor poor
__________________________________________________________________________
Tables V and VI show yet a further variety of samples in accordance with the present invention and the properties thereof.
TABLE V
__________________________________________________________________________
FORMULATION
Ingredients
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
__________________________________________________________________________
Gantrez AN-169
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
5
Gantrez AN-139
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
Gantrez AN-119
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
Glycerol 25
25
25
25
25
25
25
25
25
25
25
25
25
25
50
25
10
Water 25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
10
Igepal CO-210
--
25
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
Igepal CO-520
--
--
25
--
--
--
--
--
--
--
--
--
--
--
--
--
--
Igepal CO-630
--
--
--
25
--
--
--
--
--
--
--
--
--
--
--
--
15
Igepal CO-880
--
--
--
--
25
--
--
--
--
--
--
--
--
--
--
--
--
Igepal CO-990
--
--
--
--
--
25
--
--
--
--
--
--
--
--
--
--
--
Igepal CA-630
--
--
--
--
--
--
25
--
--
--
--
--
--
--
--
--
--
Emulphor ON-870
--
--
--
--
--
--
--
--
25
--
--
--
--
--
--
--
--
Gafac LO-529
--
--
--
--
--
--
--
25
--
--
--
--
--
--
--
--
--
Pegol 400 --
--
--
--
--
--
--
--
--
--
--
25
--
--
--
--
--
Pegol 1450
--
--
--
--
--
--
--
--
--
--
25
--
--
--
--
--
--
Pegol 4000
--
--
--
--
--
--
--
--
--
25
--
--
--
--
--
--
--
Dextrin 30 AN 45
--
--
--
--
--
--
--
--
--
--
--
--
25
--
--
--
--
Sugar --
--
--
--
--
--
--
--
--
--
--
--
--
25
--
--
--
Propyleneglycol
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
25
--
Pegol F-68
25
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
--
Formulation
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
__________________________________________________________________________
Ingredients 32 33 34
35
36 37 38
39 40
41
42
43
44
__________________________________________________________________________
Gantrez AN-169
6.6
13.3
15
5
6.6
13.3
15
15 15
--
--
--
--
Gantrez AN-139
-- -- --
--
-- -- --
-- --
--
--
25
25
Gantrez AN-119
-- -- --
--
-- -- --
-- --
25
25
--
--
Glycerol 10 10 10
10
10 10 10
-- --
25
25
25
25
Water 10 10 10
10
10 10 10
12.5
20
25
25
25
25
Igepal CO-210
-- -- --
--
-- -- --
-- --
--
--
--
--
Igepal CO-520
-- -- --
--
-- -- --
-- --
--
--
--
--
Igepal CO-630
13.3
6.6
5
--
-- -- --
15 --
--
--
--
--
Igepal CO-880
-- -- --
--
-- -- --
-- --
--
--
--
--
Igepal CO-990
-- -- --
--
-- -- --
-- --
--
--
--
--
Igepal CA-630
-- -- --
--
-- -- --
-- --
--
--
--
--
Emulphor ON-870
-- -- --
--
-- -- --
-- --
--
--
--
--
Gafac LO-529 -- -- --
--
-- -- --
-- --
--
--
--
--
Pegol 400 -- -- --
--
-- -- --
-- --
--
--
--
--
Pegol 1450 -- -- --
--
-- -- --
-- --
--
--
--
--
Pegol 4000 -- -- --
--
-- -- --
-- --
--
--
--
--
Dextrin 30 AN 45
-- -- --
15
13.3
6.6
5
-- 15
--
25
--
25
Sugar -- -- --
--
-- -- --
-- --
--
--
--
--
Propyleneglycol
-- -- --
--
-- -- --
-- --
--
--
--
--
Pegol F-68 -- -- --
--
-- -- --
-- --
25
--
25
--
Formulation 32 33 34
35
36 37 38
39 40
41
42
43
44
__________________________________________________________________________
TABLE VI
__________________________________________________________________________
PROPERTIES
Adhesion
to skin Adhesion
Skin- Skin-
After
Adhesion
Adhesion
to removal
reseal
Formulation
Initial
4 hours
to glass
to paper
dressing
properties
properties
__________________________________________________________________________
15 Poor falls off
None
Good Good Poor Easy Poor
16 Poor falls off
None
Good Poor Poor Easy None
17 Good Good
Good Good Good Difficult,
Excellent
pulls hairs
18 Good Good
Good Good Good Difficult,
Excellent
pulls hairs
19 Poor None
Good Good Good Easy Good
20 Poor None
Fair Fair Poor Easy Poor
21 Good Good
Good Good Good Difficult,
Good
22 None -- None None None -- --
23 Poor None
Good Good Good Easy Good
24 Poor None
Fair Good Fair Easy Fair
25 Poor None
Good Good Good Easy Good
26 Fair None
Good Good Poor Easy Poor
27 Good None
Good Good Good Fell off
Good
28 Good None
Good Good Good Easy Good
29 Good Good
Good Good Good Firm/Easy
Good
30 Good Good
Good Good Good Firm/Easy
Good
31 Not compatible, exudate present on surface.
32 Good Good
Good Good Good Strong,
Good remove
pulls hairs
33 Good None
Good Good Good Fell off
Good
34 Not practical formulation, too thick.
35 Good Good
Good Good Good Easy, but
Good
strong bond
36 Good None
Good Good Good Easy, but
Good
strong bond
37 Good None
Good Good Fair Fell off
Good
38 Good None
Good Good Good Fell off
Good
39 Good; adhesion too high; not possible to remove from
polyethylene!
40 Good Good
Good Good Good Strong
Good
but easy
41 Good Good
Good Good Good Strong
Good
but easy
42 Good Good
Good Good Good Strong
Good but peels
but easy
43 Good None
Good Good Good Easy Good
44 Good Fair
Good Good Good Easy Good
__________________________________________________________________________
Claims (8)
1. A method for forming a composition comprising mixing a first component of a copolymer having the formula ##STR3## wherein n is such that the average molecular weight of the copolymer is from about 2×105 to 2.4×106, with a second component selected from the group consisting of polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol, wherein the amount of the first component is in the range from about 5 to 50 weight % and the amount of the second component is from about 5 to 50 weight %, based on the total weight of the composition, in the presence of water and reacting the mixture at a temperature and time period sufficient to hydrolyze or esterify the first component.
2. The method of claim 1 wherein the adhesive composition further comprises a humectant, which humectant is a compound other than the second component.
3. The method of claim 1 wherein the average molecular weight of the co-polymer is from about 1.25×106 to 2.4×106.
4. The method of claim 1 wherein the average weight of the co-polymer in the composition is from about 1.08×106 to 1.98×106.
5. A method for forming a composition by mixing a first component selected from the group consisting of polyethoxylated fatty alcohols, nonyl phenols, octyl phenols, polyethylene glycol, 1,3-butane diol, 1,4-butane diol, propylene glycol, 1,3-propane diol, and ethylene glycol, with water and maintaining said mixture at a temperature from about 25° to 70° C., adding a second component of a copolymer having the formula: ##STR4## wherein n is such that the average molecular weight of the copolymer is from about 2×105 to 2.4×106, to this mixture so as to form a uniform paste and heating the paste at a temperature of from about 70° to 95° C. in a mold having the desired shape of the ultimate element.
6. The method of claim 5 wherein the adhesive composition further comprises a humectant, which humectant is a compound other than the first component.
7. The method of claim 5 wherein the average molecular weight of the co-polymer is from about 1.25×106 to 2.4×106.
8. The method of claim 5 wherein the average weight of the co-polymer in the composition is from about 1.08×106 to 1.98×106.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/770,977 US5106914A (en) | 1989-12-22 | 1991-10-01 | Pressure sensitive adhesive compositions and elements made therefrom |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/455,953 US5104926A (en) | 1989-12-22 | 1989-12-22 | Pressure sensitive adhesive compositions and elements made therefrom |
| US07/770,977 US5106914A (en) | 1989-12-22 | 1991-10-01 | Pressure sensitive adhesive compositions and elements made therefrom |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/455,953 Division US5104926A (en) | 1989-12-22 | 1989-12-22 | Pressure sensitive adhesive compositions and elements made therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5106914A true US5106914A (en) | 1992-04-21 |
Family
ID=27038034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/770,977 Expired - Lifetime US5106914A (en) | 1989-12-22 | 1991-10-01 | Pressure sensitive adhesive compositions and elements made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US5106914A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019390A1 (en) * | 1991-04-26 | 1992-11-12 | Isp Investments Inc. | Continuous process for the production of pressure sensitive adhesive mass compositions and articles made therefrom |
| GB2285048A (en) * | 1993-12-21 | 1995-06-28 | Sandoz Ltd | Copolymers of polyether semiesters of maleic acid |
| US5872160A (en) * | 1997-03-27 | 1999-02-16 | The Procter &Gamble Company | Denture stabilizing compositions |
| US20070149642A1 (en) * | 2005-12-28 | 2007-06-28 | Sunstar, Inc. | Denture fixative composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917573A (en) * | 1972-09-28 | 1975-11-04 | American Cyanamid Co | Process for the preparation of water emulsifiable anionic resins and the resins thus produced |
| GB2062663A (en) * | 1979-10-24 | 1981-05-28 | Hollister Inc | Protective Adhesive Paste for use with Ostomy Appliances |
-
1991
- 1991-10-01 US US07/770,977 patent/US5106914A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3917573A (en) * | 1972-09-28 | 1975-11-04 | American Cyanamid Co | Process for the preparation of water emulsifiable anionic resins and the resins thus produced |
| GB2062663A (en) * | 1979-10-24 | 1981-05-28 | Hollister Inc | Protective Adhesive Paste for use with Ostomy Appliances |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019390A1 (en) * | 1991-04-26 | 1992-11-12 | Isp Investments Inc. | Continuous process for the production of pressure sensitive adhesive mass compositions and articles made therefrom |
| US5239017A (en) * | 1991-04-26 | 1993-08-24 | Isp Investments Inc. | Continuous process for the production of pressure sensitive adhesive mass compositions and articles made therefrom |
| GB2285048A (en) * | 1993-12-21 | 1995-06-28 | Sandoz Ltd | Copolymers of polyether semiesters of maleic acid |
| US5665842A (en) * | 1993-12-21 | 1997-09-09 | Mbt Holding Ag | Organic compounds |
| US5668195A (en) * | 1993-12-21 | 1997-09-16 | Mbt Holding Ag | Fluidifying agents for cementitious compositions based random copolymers, compositions comprising the same, and methods for their use |
| GB2285048B (en) * | 1993-12-21 | 1998-04-15 | Sandoz Ltd | Addition polymer |
| US5872160A (en) * | 1997-03-27 | 1999-02-16 | The Procter &Gamble Company | Denture stabilizing compositions |
| US20070149642A1 (en) * | 2005-12-28 | 2007-06-28 | Sunstar, Inc. | Denture fixative composition |
| US7517920B2 (en) | 2005-12-28 | 2009-04-14 | Sunstar Inc. | Denture fixative composition |
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